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BBi is Zincblende, Sphalerite structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. B3- is bonded to four equivalent Bi3+ atoms to form corner-sharing BBi4 tetrahedra. All B–Bi bond lengths are 2.40 Å. Bi3+ is bonded to four equivalent B3- atoms to form corner-sharing BiB4 tetrahedra.
B6Bi is Calcium hexaboride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. B is bonded in a 5-coordinate geometry to five equivalent B and four equivalent Bi atoms. There is one shorter (1.70 Å) and four longer (1.78 Å) B–B bond length. All B–Bi bond lengths are 3.10 Å. Bi is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms.
BBi is Wurtzite structured and crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. B3- is bonded to four equivalent Bi3+ atoms to form corner-sharing BBi4 tetrahedra. There are three shorter (2.39 Å) and one longer (2.40 Å) B–Bi bond lengths. Bi3+ is bonded to four equivalent B3- atoms to form corner-sharing BiB4 tetrahedra.